CN103420932A - Method for preparing 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate - Google Patents
Method for preparing 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate Download PDFInfo
- Publication number
- CN103420932A CN103420932A CN2013103756251A CN201310375625A CN103420932A CN 103420932 A CN103420932 A CN 103420932A CN 2013103756251 A CN2013103756251 A CN 2013103756251A CN 201310375625 A CN201310375625 A CN 201310375625A CN 103420932 A CN103420932 A CN 103420932A
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- solvent
- tertiary butyl
- add
- dimethyl benzyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C1C*=*CC1 Chemical compound C1C*=*CC1 0.000 description 1
Images
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a method for preparing 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate. The method includes the following steps: first, adding cyanuric acid trisodium salt and 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl into a polar aprotic solvent, second, adding a phase transfer catalyst, third, heating the mixture to 100-120 DEG C and leaving the mixture to carry out thermal reaction for 8-20h under the protection of nitrogen, fourth, cooling the mixture to 50-60 DEG C and filtering out the salt, fifth, distilling off the solvent under a pressure of 0.005-0.015MPa, sixth, adding a non-polar solvent and water for solution and washing, seventh, distilling off residual water and a large part of solvent after settlement water diversion, eighth, adding methyl alcohol for dissolution, ninth, adding activated carbon for decoloration, tenth, cooling filtrate to achieve separation by crystallization after hot filtration, and eleventh, carrying out filtration to obtain the 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate. The method simplifies production operation processes and reduces cost for the treatment of three wastes greatly.
Description
Technical field
The present invention relates to macromolecular material auxiliary agent field, is a kind of 1,3, and the preparation method of 5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates belongs to the technology of preparing of antioxidant.
Background technology
1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates refers in particular to following formula (I):
Above formula (I) is efficient hindered phenol primary antioxidant, has and does not pollute, and non-staining characteristics, be applicable to polypropylene, polyethylene, polymeric amide, polystyrene, ABS resin, polyester, fibre resin etc., is particularly useful for polypropylene.This product is only used the 0.02-0.1% consumption can effectively suppress its thermal-oxidative degradation in high temperature process and use procedure, with the phosphorous acid esters auxiliary anti-oxidant and with having excellent synergistic effect.
The method that U.S. Cyanamid company is described in the patent US3723427 of application in 1971 is: the tricyanic acid that adds 3.23g (0.025mol) in reactor, 16.9g the tertiary butyl of 4-(0.075mol)-3-hydroxyl-2, 6-dimethyl benzyl chlorine and 50ml dimethyl formamide, splash into the triethylamine of 12ml (0.08mol) under 40 ℃, after reaction mixture stirs 18 hours again, add 50ml water and 50ml benzene, two are separated, benzene is used twice of 50ml water washing mutually, benzole soln is clarified with 50 gram superfiltrols, residuary water and benzene azeotropic shift out, add again 50ml methyl alcohol, with cooling after the 10g decolorizing with activated carbon, obtain the product of 12g, 150 ℃ of fusing points, the fusing point that recrystallization obtains sample from methyl alcohol again is 154～155 ℃.
Japan Chemipro Kasei Ltd is the preparation process of describing like this above formula (I) in the patent JP2004123609 of application in 2002: in the reactor with stirring, add the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl chlorine 67.6g (0.3mol), cyanuric acid 12.9g (0.1mol), the 200ml dimethyl formamide, be uniformly mixed, splash into triethylamine 30.4g (0.3mol), reaction mixture stirs 20 hours at 120 ℃ again, add benzene 150ml and water 150ml, two are separated, benzene is washed mutually, the clarification of benzole soln heat filtering, distill out benzene after dehydration, add the 200ml hexanaphthene, with crystallisation by cooling after 10g decolorizing with activated carbon heat filtering, separate out, obtain 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates.
The reaction formula of above-mentioned 2 patents can be represented by the formula:
This method has been used the organic basess such as triethylamine of higher price, produced the waste water that contains in a large number triethylamine hydrochloride, although can reclaim by usual method the organic basess such as triethylamine applies mechanically, but complex disposal process, in order to reach recycled requirement quality, to be spent processing cost high, thereby causing the increase of production cost, is uneconomic method.
Summary of the invention
The object of the present invention is to provide a kind of 1,3, the preparation method of 5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates, the method process is simple, has reduced three-waste pollution, has reduced preparation cost.
The present invention is achieved by following technical proposals:
A kind of 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) preparation method of chlorinated isocyanurates, it is characterized in that, by trisodium cyanurate and the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl chlorine joins in polar aprotic solvent, add phase-transfer catalyst, under nitrogen protection, be warming up to 100～120 ℃ of insulation reaction 8～20h, stopped reaction, then be cooled to 50～60 ℃ and filter out salt, distilling off solvent under the pressure of 0.005～0.015MPa, add non-polar solvent and water dissolution washing, after standing minute water, distill out residual moisture and most of solvent, add again dissolve with methanol, add activated carbon decolorizing, after heat filtering, the filtrate decrease temperature crystalline is separated out, filter, obtain 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) tricarbimide ester products.
Described raw material trisodium cyanurate and the 4-tertiary butyl-3-hydroxyl-2, mole proportioning of 6-dimethyl benzyl chlorine is 1:(3.1～3.3).
The consumption of described phase-transfer catalyst is 5～10% of trisodium cyanurate quality.
Described phase-transfer catalyst is 15-crown ether-5.
Described polar aprotic solvent is DMF or N,N-dimethylacetamide.
Described non-polar solvent is toluene or dimethylbenzene.
The invention has the advantages that, use trisodium cyanurate and the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl chlorine is that raw material prepares 1,3, white or the off-white color product of 5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates, do not re-use the organic amines such as triethylamine, simplify the production operation process, thereby made production cost be reduced.Simultaneously in the inventive method, the by product sodium-chlor major part that reaction generates filters out with the form of solid, only have minute quantity to enter into water, only need can realize qualified discharge to the low-cost simple process of waste water, thereby significantly reduce the cost of the disposal of three wastes.
Reaction formula of the present invention can be represented by the formula:
The accompanying drawing explanation
Fig. 1: be the present invention 1,3, the infrared spectrogram of 5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates;
Fig. 2: be in SciFinderScholar 1,3, the standard infrared spectrogram of 5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates.
In following examples, the fusing point of products therefrom is in 154～161 ℃ of scopes, and liquid chromatographic detection purity appearance time is identical, can determine it is same substance.
Embodiment
With embodiment, the present invention will be described as follows.Yet, absolutely not in all senses, limit the present invention's meaning.
In the 500ml four-hole bottle with agitator, reflux exchanger, thermometer; add trisodium cyanurate 19.8g(0.1mol); the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl chlorine 71g (0.31mol); DMF 200ml and phase-transfer catalyst 1g, continue to pass into nitrogen protection; stirring is warming up to 120 ℃, insulation reaction 14h.Then be cooled to 50～60 ℃ of filtrations, filtrate underpressure distillation under 0.005～0.015MPa pressure goes out N, dinethylformamide, add 200ml toluene and 100ml water in residuum, stirring is warming up to material and dissolves fully, the standing water that separates, organic phase distills out residual moisture and about 160ml toluene, slowly in residuum, add methyl alcohol 150ml, material dissolution under stirring and refluxing, add the 5g activated carbon decolorizing, after heat filtering, decrease temperature crystalline is separated out, filter, use washed with methanol, obtain 1 of drying, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates 54.6g, 157～160 ℃ of fusing points, purity 98.3%, products therefrom is correct through the infrared spectrum characterization structure.
Embodiment 2
In the four-hole bottle identical with embodiment 1; add trisodium cyanurate 19.8g (0.1mol); the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl chlorine 71g (0.31mol); N,N-dimethylacetamide 200ml and phase-transfer catalyst 1g, continue to pass into nitrogen protection; stirring is warming up to 120 ℃, insulation reaction 14h.Then be cooled to 50～60 ℃ of filtrations, filtrate underpressure distillation under 0.005～0.015MPa pressure goes out N, the N-N,N-DIMETHYLACETAMIDE, add 200ml dimethylbenzene and 100ml water in residuum, stirring is warming up to material and dissolves fully, the standing water that separates, organic phase distills out residual moisture and about 150ml dimethylbenzene, slowly in residuum, add methyl alcohol 150ml, material dissolution under stirring and refluxing, add the 5g activated carbon decolorizing, after heat filtering, decrease temperature crystalline is separated out, filter, use washed with methanol, obtain 1 of drying, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates 52.5g, 155～159 ℃ of fusing points, purity 98.1%.
Embodiment 3
In the four-hole bottle identical with embodiment 1; add trisodium cyanurate 19.8g(0.1mol); the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl chlorine 75.5g(0.33mol); DMF 200ml and phase-transfer catalyst 2g, continue to pass into nitrogen protection; stirring is warming up to 100 ℃, insulation reaction 20h.Then be cooled to 50～60 ℃ of filtrations, filtrate underpressure distillation under 0.005～0.015MPa pressure goes out N, dinethylformamide, add 200ml toluene and 100ml water in residuum, stirring is warming up to material and dissolves fully, the standing water that separates, organic phase distills out residual moisture and about 160ml toluene, slowly in residuum, add methyl alcohol 150ml, material dissolution under stirring and refluxing, add the 5g activated carbon decolorizing, decrease temperature crystalline is separated out, filter, use washed with methanol, obtain 1 of drying, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates 50.8g, 154～157 ℃ of fusing points, purity 98%.
Embodiment 4
In the four-hole bottle identical with embodiment 1; add trisodium cyanurate 19.8g(0.1mol); the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl chlorine 73.2g(0.32mol); DMF 200ml and phase-transfer catalyst 1.5g, continue to pass into nitrogen protection; stirring is warming up to 120 ℃, insulation reaction 14h.Then be cooled to 50～60 ℃ of filtrations, filtrate underpressure distillation under 0.005～0.015MPa pressure goes out N, dinethylformamide, add 200ml toluene and 100ml water in residuum, stirring is warming up to material and dissolves fully, the standing water that separates, organic phase distills out residual moisture and about 160ml toluene, slowly in residuum, add methyl alcohol 150ml, material dissolution under stirring and refluxing, add the 5g activated carbon decolorizing, decrease temperature crystalline is separated out, filter, use washed with methanol, obtain 1 of drying, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates 57.2g, 158～161 ℃ of fusing points, purity 99.1%.
Embodiment 5
In the four-hole bottle identical with embodiment 1; add trisodium cyanurate 19.8g(0.1mol); the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl chlorine 75.5g(0.33mol); DMF 200ml and phase-transfer catalyst 1.5g, continue to pass into nitrogen protection; stirring is warming up to 120 ℃, insulation reaction 8h.Then be cooled to 50～60 ℃ of filtrations, filtrate underpressure distillation under 0.005～0.015MPa pressure goes out N, dinethylformamide, add 200ml toluene and 100ml water in residuum, stirring is warming up to material and dissolves fully, the standing water that separates, organic phase distills out residual moisture and about 160ml toluene, slowly in residuum, add methyl alcohol 150ml, material dissolution under stirring and refluxing, add the 5g activated carbon decolorizing, decrease temperature crystalline is separated out, filter, use washed with methanol, obtain 1 of drying, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates 55g, 157～160 ℃ of fusing points, purity 98.8%.
Embodiment 6
In the four-hole bottle identical with embodiment 1; add trisodium cyanurate 19.8g(0.1mol); the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl chlorine 73.2g(0.32mol); DMF 200ml and phase-transfer catalyst 1.5g, continue to pass into nitrogen protection; stirring is warming up to 110 ℃, insulation reaction 20h.Then be cooled to 50～60 ℃ of filtrations, filtrate underpressure distillation under 0.005～0.015MPa pressure goes out N, dinethylformamide, add 200ml dimethylbenzene and 100ml water in residuum, stirring is warming up to material and dissolves fully, the standing water that separates, organic phase distills out residual moisture and about 160ml dimethylbenzene, slowly in residuum, add methyl alcohol 150ml, material dissolution under stirring and refluxing, add the 5g activated carbon decolorizing, decrease temperature crystalline is separated out, filter, use washed with methanol, obtain 1 of drying, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) chlorinated isocyanurates 57g, 157～161 ℃ of fusing points, purity 98.9%.
Repeat the technology and condition of embodiment 4, the present embodiment technology and condition different from embodiment 4 is: use 200mlN, the N-N,N-DIMETHYLACETAMIDE replaces 200mlN, dinethylformamide, and other condition and operating process are identical, finally obtain 1 of drying, 3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates 54g, 155～158 ℃ of fusing points, purity 98.5%.
Claims (6)
1. one kind 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) preparation method of chlorinated isocyanurates, it is characterized in that, by trisodium cyanurate and the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl chlorine joins in polar aprotic solvent, add phase-transfer catalyst, under nitrogen protection, be warming up to 100～120 ℃ of insulation reaction 8～20h, stopped reaction, then be cooled to 50～60 ℃ and filter out salt, distilling off solvent under the pressure of 0.005～0.015MPa, add non-polar solvent and water dissolution washing, after standing minute water, distill out residual moisture and most of solvent, add again dissolve with methanol, add activated carbon decolorizing, after heat filtering, the filtrate decrease temperature crystalline is separated out, filter, obtain 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) tricarbimide ester products.
2. method according to claim 1, is characterized in that described raw material trisodium cyanurate and the 4-tertiary butyl-3-hydroxyl-2, and mole proportioning of 6-dimethyl benzyl chlorine is 1:(3.1～3.3).
3. method according to claim 1, the consumption that it is characterized in that described phase-transfer catalyst is 5～10% of trisodium cyanurate quality.
4. method according to claim 1, is characterized in that described phase-transfer catalyst is 15-crown ether-5.
5. method according to claim 1, is characterized in that described polar aprotic solvent is DMF or N,N-dimethylacetamide.
6. method according to claim 1, is characterized in that described non-polar solvent is toluene or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310375625.1A CN103420932B (en) | 2013-08-26 | 2013-08-26 | The preparation method of 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310375625.1A CN103420932B (en) | 2013-08-26 | 2013-08-26 | The preparation method of 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103420932A true CN103420932A (en) | 2013-12-04 |
| CN103420932B CN103420932B (en) | 2016-02-17 |
Family
ID=49646358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310375625.1A Active CN103420932B (en) | 2013-08-26 | 2013-08-26 | The preparation method of 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103420932B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661710A (en) * | 2021-01-25 | 2021-04-16 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1790 |
| CN115246792A (en) * | 2021-09-26 | 2022-10-28 | 佳化化学科技发展（上海）有限公司 | Method for purifying tris (2-hydroxyethyl) isocyanurate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723427A (en) * | 1971-11-16 | 1973-03-27 | American Cyanamid Co | Hindered tris(meta-hydroxybenzyl)cyanurate antioxidants |
| JP2004123609A (en) * | 2002-10-02 | 2004-04-22 | Chemiprokasei Kaisha Ltd | New crystal modification, method for producing the same, antioxidant using the same, resin composition containing the antioxidant and molding thereof |
| CN1888014A (en) * | 2006-06-05 | 2007-01-03 | 南京师范大学 | Synthesis of fire retardant tri (bromophenoxy) cyanurate |
| CN1923821A (en) * | 2006-09-28 | 2007-03-07 | 宜兴市中正化工有限公司 | Synthesis method of trihydroxyethyl isocyanuric ester |
| CN102030717A (en) * | 2010-11-05 | 2011-04-27 | 合肥工业大学 | Synthesis method and application of trialkynyl monomer 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-triketone |
| CN102127025A (en) * | 2010-12-13 | 2011-07-20 | 岳阳昌德化工实业有限公司 | Tri(2-hydroxyl cyclohexyl) isocyanurate as well as preparation method and application thereof |
| CN102924392A (en) * | 2012-11-07 | 2013-02-13 | 山东润科化工股份有限公司 | One-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate |
-
2013
- 2013-08-26 CN CN201310375625.1A patent/CN103420932B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723427A (en) * | 1971-11-16 | 1973-03-27 | American Cyanamid Co | Hindered tris(meta-hydroxybenzyl)cyanurate antioxidants |
| JP2004123609A (en) * | 2002-10-02 | 2004-04-22 | Chemiprokasei Kaisha Ltd | New crystal modification, method for producing the same, antioxidant using the same, resin composition containing the antioxidant and molding thereof |
| CN1888014A (en) * | 2006-06-05 | 2007-01-03 | 南京师范大学 | Synthesis of fire retardant tri (bromophenoxy) cyanurate |
| CN1923821A (en) * | 2006-09-28 | 2007-03-07 | 宜兴市中正化工有限公司 | Synthesis method of trihydroxyethyl isocyanuric ester |
| CN102030717A (en) * | 2010-11-05 | 2011-04-27 | 合肥工业大学 | Synthesis method and application of trialkynyl monomer 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-triketone |
| CN102127025A (en) * | 2010-12-13 | 2011-07-20 | 岳阳昌德化工实业有限公司 | Tri(2-hydroxyl cyclohexyl) isocyanurate as well as preparation method and application thereof |
| CN102924392A (en) * | 2012-11-07 | 2013-02-13 | 山东润科化工股份有限公司 | One-pot method for preparing 1,3,5-three (five-bromine benzyl) isocyanurate |
Non-Patent Citations (1)
| Title |
|---|
| 彭敏等: "三(环氧丙基)异氰尿酸酯的合成", 《热固性树脂》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661710A (en) * | 2021-01-25 | 2021-04-16 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1790 |
| CN112661710B (en) * | 2021-01-25 | 2021-10-29 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1790 |
| CN115246792A (en) * | 2021-09-26 | 2022-10-28 | 佳化化学科技发展（上海）有限公司 | Method for purifying tris (2-hydroxyethyl) isocyanurate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103420932B (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20200061948A (en) | Purification of bis-2-hydroxyethyl terephthalate and preparation of polyester by using the same | |
| CN102775364B (en) | Preparation method of cross linking agent triallyl isocyanurate | |
| CN111170872B (en) | Method for purifying p-phenylenediamine | |
| CN103435604A (en) | Refining method of high-purity azilsartan | |
| SK8892003A3 (en) | Obtaining anthracene and carbazole by melt-crystallization | |
| CN103420932A (en) | Method for preparing 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate | |
| CN108586206B (en) | Method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by one-pot method | |
| KR101986367B1 (en) | Recovery method of the organic solution from the waste result solution of polyimide production process and its production system | |
| CN101967085A (en) | Method for recycling ditrimethylolpropane | |
| CN103539747A (en) | Preparation method of 4,6-dichloropyrimidine | |
| CN102653525A (en) | Preparing bendamustine alkyl ester compounds, comprises reacting substituted 2-((2-hydroxy-ethyl)-phenyl-amino)-ethanol compounds with a mixture comprising carbonyl amine compounds and sulfonyl compounds, or diketo compounds | |
| CN104478747B (en) | A kind of method utilizing organic solvent to produce glycine | |
| CN102898345A (en) | Preparation method of N-(2, 4, 6-trichlorophenyl) maleimide | |
| CN103467252A (en) | Method for increasing purity of di-trimethylolpropane | |
| CN112661710B (en) | Synthesis method of antioxidant 1790 | |
| CN112441960B (en) | Synthetic method of sulpiride | |
| CN109879762A (en) | A kind of method of purification of o-phenylenediamine | |
| CN105384654B (en) | A kind of crystallization purifications of hydroxyalkyl amide | |
| CN108409536B (en) | Method for recovering pentaerythritol from alcohol hydrolysis liquid filter residue of antioxidant 1010 mother liquor | |
| CN112920036A (en) | Improved refining process of 1, 4-dihydroxy anthraquinone | |
| CN101333167A (en) | Separating and purifying method for catabolite of polyethylene terephthalate | |
| CN102718728B (en) | Refining process of rubber vulcanization accelerator MBT | |
| CN102786400A (en) | Purification method for ultraviolet absorbent 2,4-dihydroxy benaophenonel | |
| JPH0485366A (en) | Manufacture of rhodamine | |
| CN1241919C (en) | Method for purifying compound of anhydrides aromatic carboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |